KR20070026854A - Pressure-sensitive adhesive composition - Google Patents
Pressure-sensitive adhesive composition Download PDFInfo
- Publication number
- KR20070026854A KR20070026854A KR1020077001768A KR20077001768A KR20070026854A KR 20070026854 A KR20070026854 A KR 20070026854A KR 1020077001768 A KR1020077001768 A KR 1020077001768A KR 20077001768 A KR20077001768 A KR 20077001768A KR 20070026854 A KR20070026854 A KR 20070026854A
- Authority
- KR
- South Korea
- Prior art keywords
- block copolymer
- sensitive adhesive
- pressure
- adhesive composition
- composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 76
- 229920001400 block copolymer Polymers 0.000 claims abstract description 118
- -1 diene compound Chemical class 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000004793 Polystyrene Substances 0.000 claims abstract description 6
- 229920002223 polystyrene Polymers 0.000 claims abstract description 6
- 150000001993 dienes Chemical group 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 67
- 150000001491 aromatic compounds Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 62
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000012943 hotmelt Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000002900 organolithium compounds Chemical class 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- NLRVQGZDJHUKOM-UHFFFAOYSA-N 6-methyl-4,6-bis(octylsulfanylmethoxy)cyclohexa-1,3-dien-1-ol Chemical compound C(CCCCCCC)SCOC1(CC(=CC=C1O)OCSCCCCCCCC)C NLRVQGZDJHUKOM-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 125000002897 diene group Chemical group 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- QGVHVMGAUSCKGU-UHFFFAOYSA-N 4,6-bis(dodecylsulfanylmethoxy)-6-methylcyclohexa-1,3-dien-1-ol Chemical compound C(CCCCCCCCCCC)SCOC1(CC(=CC=C1O)OCSCCCCCCCCCCCC)C QGVHVMGAUSCKGU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- DWUSYXYBLHQJBV-UHFFFAOYSA-N 6-tert-butyl-3-methyl-2,4-bis(phenylsulfanylmethyl)phenol Chemical compound C1=C(C(C)(C)C)C(O)=C(CSC=2C=CC=CC=2)C(C)=C1CSC1=CC=CC=C1 DWUSYXYBLHQJBV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CFAQEGIOZRMVET-UHFFFAOYSA-N C(CC(C)C)OCCC(C)C.[K] Chemical compound C(CC(C)C)OCCC(C)C.[K] CFAQEGIOZRMVET-UHFFFAOYSA-N 0.000 description 1
- JYFDOMBDCAQMJN-UHFFFAOYSA-N CCCCCCCCC[P]C1=CC=CC=C1 Chemical class CCCCCCCCC[P]C1=CC=CC=C1 JYFDOMBDCAQMJN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- MXFRWBNCSXHXRE-UHFFFAOYSA-N [Li]\C=C\C Chemical compound [Li]\C=C\C MXFRWBNCSXHXRE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JFHGLVIOIANSIN-UHFFFAOYSA-N dimethyl butanedioate;1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound COC(=O)CCC(=O)OC.CC1(C)CC(O)CC(C)(C)N1CCO JFHGLVIOIANSIN-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical class [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- CSWFWSPPZMEYAY-UHFFFAOYSA-N octadecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)O CSWFWSPPZMEYAY-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Abstract
Description
본 발명은 감압성 접착제 조성물에 관한 것이다. 특히, 저온 가공성이 우수하고, 외관, 감압성 접착제 성능, 내열성이 지극히 우수한 감압성 접착제 조성물에 관한 것이다.The present invention relates to pressure sensitive adhesive compositions. In particular, it is related with the pressure-sensitive adhesive composition excellent in low-temperature workability and extremely excellent in external appearance, pressure-sensitive adhesive performance, and heat resistance.
근래, 에너지 절약, 자원 절약, 환경 부담 감소 등을 위하여, 핫 멜트형 감압성 접착제가 널리 이용되고 있으며, 이러한 핫 멜트형 감압성 접착제의 베이스 폴리머로서, 모노알케닐 방향족 화합물과 공액(conjugate) 디엔 화합물로 이루어진 블록 공중합체(SBS, SlS 등)가 널리 사용되고 있다. 그러나, 이들 블록 공중합체를 사용해서 얻어지는 감압성 접착제 조성물은, 유지력, 택(tack) 성능, 가공성의 밸런스가 충분하지 않기 때문에, 이들의 개량이 요망되어 왔다. 이를 개량하기 위한 방법으로서, 예를 들면, 일본 특개 소 61-278578호 공보에는, 트리 블록 공중합체와 디 블록 공중합체로 이루어진 감압성 접착제 조성물이 개시되어 있다. 또한, 일본 특개 소 63-248817호 공보에는, 특정 2작용성 커플링제(특정 디할로겐 화합물)로 커플링시켜서 얻어진 블록 공중합체로 이루어진 감압성 접착제 조성물이 개시되어 있다.Recently, in order to save energy, save resources, and reduce the environmental burden, hot melt pressure sensitive adhesives are widely used. As base polymers of such hot melt pressure sensitive adhesives, monoalkenyl aromatic compounds and conjugated dienes are used. Block copolymers of compounds (SBS, SlS, etc.) are widely used. However, since the pressure-sensitive adhesive composition obtained by using these block copolymers does not have sufficient balance of holding force, tack performance and processability, these improvements have been desired. As a method for improving this, for example, Japanese Patent Laid-Open No. 61-278578 discloses a pressure-sensitive adhesive composition composed of a triblock copolymer and a diblock copolymer. In addition, Japanese Patent Laid-Open No. 63-248817 discloses a pressure-sensitive adhesive composition composed of a block copolymer obtained by coupling with a specific difunctional coupling agent (specific dihalogen compound).
특허 문헌 1: 일본 특개 소 61-278578호 공보Patent Document 1: Japanese Patent Application Laid-Open No. 61-278578
특허 문헌 2: 일본 특개 소 63-248817호 공보Patent Document 2: Japanese Patent Application Laid-Open No. 63-248817
하지만, 최근, 핫 멜트 감압성 접착제에 대하여 성능의 고도화, 복잡화가 요구되고 있으며, 예를 들면, 종이 기저귀, 냅킨 등의 위생 재료와 관련하여 사용되는 감압성 접착제에서는, 외관, 위생성이나 가공성을 위하여, 투명성, 내열변색성, 악취 및 저점도화 등, 여러 가지 면에서 우수한 성능이 요구되고 있다. 또한, 감압성 접착제 도포 기술의 개량이나 이에 따른 최종 제품의 생산성 향상이 필요하기 때문에, 감압성 접착제 조성물의 저점도화, 특히 피착체의 강도 유지를 위하여, 저온에서의 도포성이 우수한 핫 멜트형 감압성 접착제가 요구되고 있다.However, in recent years, the hot melt pressure-sensitive adhesive has been required to increase the performance and complexity, for example, in the pressure-sensitive adhesive used in connection with sanitary materials such as paper diapers, napkins, for the appearance, hygiene and processability Excellent performance is required in various aspects, such as transparency, heat discoloration resistance, odor and low viscosity. In addition, since it is necessary to improve the pressure-sensitive adhesive coating technology and thereby improve the productivity of the final product, in order to reduce the viscosity of the pressure-sensitive adhesive composition, in particular, to maintain the strength of the adherend, hot melt pressure reduction excellent in coating property at low temperature Sex adhesives are required.
하지만, 예를 들면, SBS는, 공액 디엔 연쇄에 비닐 결합이 포함되므로 일반적으로 내열성이 뒤떨어지고, 예를 들면, 고온에서 감압성 접착제를 저점도화해서 가공성을 높일 경우, 열변색되거나, 겔화, 열분해 등에 의하여 감압성 접착제 조성물의 외관이 손상되거나, 감압성 접착제 성능이 저하된다. 한편, 이러한 열변색, 열열화를 억제하기 위하여 감압성 접착제 조성물을 저온에서 가공할 경우, 용융 점도가 높아지고, 가공이 곤란해진다. 또한, 가공성이 문제가 될 경우, 이를 개량하기 위해서 연화제를 많이 첨가하는 방법이나 블록 공중합체의 배합량을 줄이는 방법이 채용되는 경우가 있지만, 이러한 방법은, 감압성 접착제 성능의 밸런스의 저하를 초래하거나, 연화제의 블리딩(bleeding)을 생성시켜서, 감압성 접착제 조성물의 외관, 위생성이 저하되는 경우가 많다. 또한, 단순히 SBS의 분자량을 낮출 경우, 얻어지는 감압성 접착제의 열변색성이나 가공성은 개선시킬 수 있지만, 감압성 접착제 성능이 극단적으로 저하되므로 바람직하지 않다.However, SBS, for example, is generally inferior in heat resistance because the conjugated diene chain includes vinyl bonds. For example, when SBS lowers the pressure-sensitive adhesive at high temperatures to increase workability, it is thermally discolored, gelled, or pyrolyzed. The appearance of the pressure-sensitive adhesive composition may be impaired, or the pressure-sensitive adhesive performance may be deteriorated. On the other hand, when processing a pressure-sensitive adhesive composition at low temperature in order to suppress such thermal discoloration and thermal deterioration, melt viscosity becomes high and processing becomes difficult. Moreover, when workability becomes a problem, in order to improve this, the method of adding a lot of softening agent or the method of reducing the compounding quantity of a block copolymer may be employ | adopted, but such a method leads to the fall of the balance of pressure-sensitive adhesive performance, In some cases, bleeding of the softener is generated, and the appearance and hygiene of the pressure-sensitive adhesive composition are often lowered. In addition, when the molecular weight of SBS is simply lowered, the thermochromic property and workability of the pressure-sensitive adhesive obtained can be improved, but the pressure-sensitive adhesive performance is extremely lowered, which is not preferable.
본 발명은, 상기와 같은 종래의 감압성 접착제 조성물과 관련된 문제를 해결하고, 특히, 저온 가공성이 우수하며, 외관, 감압성 접착제 성능, 내열성이 지극히 우수한 감압성 접착제 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to solve the problems associated with the conventional pressure-sensitive adhesive composition as described above, and in particular, to provide a pressure-sensitive adhesive composition that is excellent in low temperature processability and extremely excellent in appearance, pressure-sensitive adhesive performance, and heat resistance. .
본 발명자들은 상기 과제를 해결하기 위한 검토를 거듭한 결과, 어떤 특정한 모노알케닐 방향족 화합물과 공액 디엔 화합물의 블록 공중합체 조성물을 함유하는 점착제 조성물이, 저온 가공성이 지극히 우수하고, 상기 목적을 달성할 수 있음을 발견함으로써, 본 발명을 완성하게 되었다.MEANS TO SOLVE THE PROBLEM As a result of repeating examination for solving the said subject, the adhesive composition containing the block copolymer composition of a specific monoalkenyl aromatic compound and a conjugated diene compound is extremely excellent in low temperature workability, and can achieve the said objective. By discovering that the present invention can be completed, the present invention has been completed.
즉, 본 발명은, 하기 점착제 조성물을 제공함으로써 상기 목적을 달성했다.That is, this invention achieved the said objective by providing the following adhesive composition.
(A) 블록 공중합체 조성물을 포함하는 감압성 접착제 조성물로서,(A) A pressure sensitive adhesive composition comprising the block copolymer composition,
상기 블록 공중합체 조성물(A)은 모노알케닐 방향족 화합물을 주체로 하는 2개 이상의 중합체 블록과 공액 디엔 화합물을 주체로 하는 하나 이상의 중합체 블록으로 이루어진 블록 공중합체(a)와, 모노알케닐 방향족 화합물을 주체로 하는 하나 이상의 중합체 블록과 공액 디엔 화합물을 주체로 하는 하나 이상의 중합체 블록으로 이루어진 블록 공중합체(b)를 포함하며,The block copolymer composition (A) is a block copolymer (a) consisting of two or more polymer blocks mainly composed of monoalkenyl aromatic compounds and one or more polymer blocks mainly composed of conjugated diene compounds, and monoalkenyl aromatic compounds. A block copolymer (b) consisting of at least one polymer block mainly composed of and at least one polymer block mainly composed of a conjugated diene compound,
상기 블록 공중합체(a)의 GPC 측정에 의한 피크 분자량이 표준 폴리스티렌 환산으로 6만∼11만이며,The peak molecular weight by GPC measurement of the block copolymer (a) is 60,000 to 110,000 in terms of standard polystyrene,
상기 블록 공중합체 조성물(A)을 구성하는, 상기 모노알케닐 방향족 화합물을 주체로 하는 중합체 블록의 피크 분자량은, 1만∼3만, 분자량 분포(Mw/Mn)는 1.0∼1.6이며,The peak molecular weight of the polymer block which mainly comprises the said monoalkenyl aromatic compound which comprises the said block copolymer composition (A) is 10,000-30,000, molecular weight distribution (Mw / Mn) is 1.0-1.6,
상기 블록 공중합체 조성물(A) 중의 상기 전체 모노알케닐 방향족 화합물 함유량은, 40중량% 초과 50중량% 이하이며,The said total monoalkenyl aromatic compound content in the said block copolymer composition (A) is more than 40 weight% and 50 weight% or less,
상기 블록 공중합체 조성물(A) 중의 상기 블록 공중합체(b)의 함유량은, 50∼90중량%이며,Content of the said block copolymer (b) in the said block copolymer composition (A) is 50 to 90 weight%,
상기 블록 공중합체 조성물(A) 중의 상기 공액 디엔 부분의 비닐 결합량은, 20% 미만이며,The vinyl bond amount of the said conjugated diene part in the said block copolymer composition (A) is less than 20%,
상기 블록 공중합체 조성물(A)의 25℃에서의 15% 톨루엔 용액 점도는, 10∼40cP인, 감압성 접착제 조성물.The pressure-sensitive adhesive composition of 15% toluene solution viscosity at 25 ° C of the block copolymer composition (A) is 10 to 40 cP.
[발명을 실시하기 위한 최선의 형태]Best Mode for Carrying Out the Invention
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명을 구성하는 (A) 성분은, 모노알케닐 방향족 화합물을 주체로 하는 최소한 2개의 중합체 블록과 공액 디엔을 주체로 하는 최소한 1개의 중합체 블록으로 이루어지는 블록 공중합체(a)와, 모노알케닐 방향족 화합물을 주체로 하는 최소한 1개의 중합체 블록과 공액 디엔 화합물을 주체로 하는 최소한 1개의 중합체 블록으로 이루어지는 블록 공중합체(b)로 이루어지는 블록 공중합체 조성물이다.(A) component which comprises this invention is a block copolymer (a) which consists of at least 2 polymer blocks mainly having a monoalkenyl aromatic compound, and at least 1 polymer block mainly having a conjugated diene, and monoalkenyl It is a block copolymer composition which consists of a block copolymer (b) which consists of at least 1 polymer block which mainly uses an aromatic compound, and at least 1 polymer block which mainly contains a conjugated diene compound.
모노알케닐 방향족 화합물을 주체로 하는 중합체 블록은, 모노알케닐 방향족 화합물 단독 중합체 블록 또는 모노알케닐 방향족 화합물을 50중량% 이상 함유하는 실질적으로 모노알케닐 방향족 화합물을 주성분으로 하는 공중합체 블록이다. 또한, 공액 디엔 화합물을 주체로 하는 중합체 블록은, 공액 디엔 화합물 단독 중합체 블록 또는 공액 디엔 화합물을 50중량% 이상 함유하는 실질적으로 공액 디엔 화합물을 주성분으로 하는 공중합체 블록이다. 공액 디엔 화합물을 주체로 하는 중합체 블록이, 예를 들면, 모노알케닐 방향족 화합물-공액 디엔 화합물의 공중합체일 경우, 공중합체 블록 중의 모노알케닐 방향족 화합물은 균일하게 분포되거나 또는 불균일(예를 들면, 테이퍼형)하게 분포될 수도 있다. 균일하게 분포된 부분 및/또는 불균일하게 분포된 부분은 각 블록에 복수로 존재해도 된다.The polymer block mainly containing a monoalkenyl aromatic compound is a monoalkenyl aromatic compound homopolymer block or the copolymer block which has a substantially monoalkenyl aromatic compound containing 50 weight% or more of monoalkenyl aromatic compounds as a main component. The polymer block mainly composed of the conjugated diene compound is a conjugated diene compound homopolymer block or a copolymer block mainly composed of a conjugated diene compound containing 50% by weight or more of the conjugated diene compound. When the polymer block mainly composed of the conjugated diene compound is, for example, a copolymer of a monoalkenyl aromatic compound-conjugated diene compound, the monoalkenyl aromatic compound in the copolymer block is uniformly distributed or nonuniform (for example, Tapered). A uniformly distributed portion and / or a nonuniformly distributed portion may be present in plural in each block.
블록 공중합체(a), (b)에 사용되는 모노알케닐 방향족 화합물로서는, 예를 들면 스티렌, p-메틸스티렌, 제3급 부틸스티렌, α-메틸스티렌, 1,1-디페닐에틸렌 등의 단량체를 들 수 있고, 이 중에서 스티렌이 바람직하다. 이들 단량체는, 단독 또는 2종 이상을 병용해도 된다.As a monoalkenyl aromatic compound used for a block copolymer (a), (b), For example, styrene, p-methylstyrene, tertiary butyl styrene, (alpha) -methylstyrene, 1, 1- diphenyl ethylene, etc. A monomer is mentioned, Among these, styrene is preferable. These monomers may use individually or in combination of 2 or more types.
한편, 공액 디엔 화합물로서는, 예를 들면, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔, 3-부틸-1,3-옥타디엔, 페닐-1,3-부타디엔 등의 단량체를 들 수 있고, 이 중에서 1,3-부타디엔 및 이소프렌이 바람직하고, 1,3-부타디엔이 가장 바람직하다. 이들 단량체는, 단독 또는 2종 이상을 병용해도 된다.Meanwhile, as the conjugated diene compound, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene and the like Monomers are mentioned, of which 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is most preferred. These monomers may use individually or in combination of 2 or more types.
또한, 블록 공중합체 조성물(A)에 포함되는 전체 결합 모노알케닐 방향족 화합물 함유량은, 블록 공중합체 조성물의 생산성·내블록킹성 및 얻어지는 감압성 접착제 조성물의 유지력 성능, 내열성의 관점에서 40중량%를 초과하고, 또한 얻어지는 감압성 접착제 조성물의 점성 성능의 관점에서 50중량% 이하이다. 40중량%를 초과하고 48중량% 이하인 것이 바람직하다.In addition, all the binding monoalkenyl aromatic compound content contained in a block copolymer composition (A) is 40 weight% from a viewpoint of the productivity and blocking resistance of a block copolymer composition, the holding performance of the pressure-sensitive adhesive composition obtained, and heat resistance. It is exceeding and it is 50 weight% or less from a viscosity performance of the pressure-sensitive adhesive composition obtained further. It is preferable that it exceeds 40 weight% and is 48 weight% or less.
본 발명의 블록 공중합체 조성물(A)을 구성하는 블록 공중합체(b)의 함유량은, 얻어지는 감압성 접착제 조성물의 용융 점도, 및 택 등의 감압성 접착제 성능의 관점에서 50중량% 이상이며, 얻어지는 블록 공중합체 조성물의 기계적 강도, 고무 탄성, 내블록킹성, 또한 얻어지는 감압성 접착제 조성물의 유지력 성능의 관점에서 90중량% 이하이다. 블록 공중합체(b)의 함유량은 55∼85중량%가 바람직하고, 60∼80중량%가 보다 바람직하다.Content of the block copolymer (b) which comprises the block copolymer composition (A) of this invention is 50 weight% or more from a viewpoint of the melt viscosity of the pressure-sensitive adhesive composition obtained, and pressure-sensitive adhesive performance, such as a tack, and is obtained It is 90 weight% or less from a viewpoint of the mechanical strength of a block copolymer composition, rubber elasticity, blocking resistance, and the holding force performance of the pressure sensitive adhesive composition obtained. 55-85 weight% is preferable and, as for content of a block copolymer (b), 60-80 weight% is more preferable.
본 발명에서는, 블록 공중합체 조성물(A)을 구성하는 블록 공중합체(b)의 함유량[b]은, 얻어지는 블록 공중합체 조성물의 생산성, 내블록킹성 및 얻어지는 감압성 접착제 조성물의 유지력 성능, 택 등의 감압성 접착제 성능의 관점에서, 하기 식을 만족시키는 것이 바람직하다.In this invention, content [b] of the block copolymer (b) which comprises a block copolymer composition (A) is the productivity, blocking resistance of the block copolymer composition obtained, the holding performance of the pressure-sensitive adhesive composition obtained, tack etc. From the viewpoint of the pressure-sensitive adhesive performance of, it is preferable to satisfy the following formula.
5[S]-175≤[b]≤5[S]-1305 [S] -175≤ [b] ≤5 [S] -130
([S]는 블록 공중합체 조성물(A) 중의 전체 모노알케닐 방향족 화합물 함유량)([S] is the total monoalkenyl aromatic compound content in the block copolymer composition (A))
블록 공중합체(a)의 피크 분자량은, 얻어지는 블록 공중합체(A)의 고무 탄성적 성질, 기계적 강도 및 얻어지는 감압성 접착제 조성물의 유지력 성능의 관점에서 표준 폴리스티렌 환산으로 60,000 이상, 얻어지는 감압성 접착제 조성물의 용융 점도, 내열성, 분산성이나 가공성의 관점에서 표준 폴리스티렌 환산으로 110,O00 이하이다. 바람직한 범위는 65,000∼105,000이다.The peak molecular weight of the block copolymer (a) is 60,000 or more in terms of standard polystyrene in view of the rubber elastic properties, mechanical strength of the block copolymer (A) obtained, and the holding force performance of the obtained pressure-sensitive adhesive composition. It is 110,00 or less in terms of standard polystyrene in terms of melt viscosity, heat resistance, dispersibility and processability. Preferable range is 65,000-105,000.
블록 공중합체 조성물을 구성하는 모노알케닐 방향족 화합물을 주체로 하는 중합체 블록의 피크 분자량은, 얻어지는 감압성 접착제 조성물의 유지력 성능의 관점에서, 10,000 이상, 점착 성능, 저온에서의 용융 점도의 관점에서 30,000 이하이다. 바람직한 범위는 10,000∼25,000이며, 보다 바람직한 범위는 12,000∼23,000이다.The peak molecular weight of the polymer block mainly composed of the monoalkenyl aromatic compound constituting the block copolymer composition is 30,000 or more from the viewpoint of the holding force performance of the pressure-sensitive adhesive composition obtained from the viewpoint of 10,000 or more, adhesion performance, and melt viscosity at low temperature. It is as follows. The preferable range is 10,000-25,000, and the more preferable range is 12,000-23,000.
또한, 블록 공중합체 조성물을 구성하는 모노알케닐 방향족 화합물을 주체로 하는 중합체 블록의 분자량 분포는, 내블록킹성 및 얻어지는 감압성 접착제 조성물의 점착력, 유지력 성능의 관점에서, 1.0∼1.6이다. 보다 바람직한 범위는 1.0∼13, 더욱 바람직하게는 1.0∼1.2이다.Moreover, the molecular weight distribution of the polymer block which mainly uses the monoalkenyl aromatic compound which comprises a block copolymer composition is 1.0-1.6 from a viewpoint of blocking resistance and the adhesive force and holding force performance of the pressure-sensitive adhesive composition obtained. More preferably, it is 1.0-13, More preferably, it is 1.0-1.2.
또한, 본 발명의 블록 공중합체 조성물의 공액 디엔 부분의 비닐 결합량은, 내열성 및 가열시의 용융 점도 변화, 가열시의 변색성의 관점에서, 20% 미만이다. 보다 바람직한 범위는 18% 미만, 더욱 바람직하게는 16% 미만이다.In addition, the vinyl bond amount of the conjugated diene part of the block copolymer composition of this invention is less than 20% from a heat resistance, the melt viscosity change at the time of a heating, and the discoloration at the time of heating. More preferred range is less than 18%, more preferably less than 16%.
본 발명의 블록 공중합체 조성물(A)의 25℃에서의 15% 톨루엔 용액 점도는 얻어지는 감압성 접착제 조성물의 점착력, 유지력 등의 감압성 접착제 성능의 관점에서 1OcP 이상이며, 얻어지는 감압성 접착제 조성물의 용융 점도, 가공성, 내열성의 관점에서 40cP 이하이다. 25℃에서의 15% 톨루엔 용액 점도는, 12∼35cP가 바람직하고, 보다 바람직하게는 15∼32cp이다.15% toluene solution viscosity in 25 degreeC of the block copolymer composition (A) of this invention is 100 cP or more from a viewpoint of pressure-sensitive adhesive performance, such as adhesive force and holding force, of the pressure-sensitive adhesive composition obtained, melting of the pressure-sensitive adhesive composition obtained It is 40 cP or less from a viewpoint of a viscosity, workability, and heat resistance. As for 15% toluene solution viscosity in 25 degreeC, 12-35 cP is preferable, More preferably, it is 15-32 cps.
본 발명을 구성하는 블록 공중합체(a) 및 (b)로 이루어지는 블록 공중합체 조성물(A)은, 예를 들면 불활성 탄화수소 용매 중에서 유기 리튬 화합물을 중합 개시제로 하여 스티렌을 중합하고, 이어서, 얻어진 중합체와 부타디엔을 중합시키고, 또한 경우에 따라서는 이들 조작을 반복하여, 2종류의 스티렌부타디엔 블록 공중합체 폴리머(a) 및 (b)를 별도로 중합하여, 혼합함으로써 얻어진다. 이때, 분자량은 유기 리튬 화합물량을 제어함으로써 조정된다. 조성물(A)의 혼합 방법은, 중합 반응 종료 후 혼합하고, 물, 알코올, 산 등을 첨가해서 활성종을 비활성화, 또는 중합 반응 종료 후, 블록 공중합체(a), (b)의 용액을 별도로 비활성화하고, 혼합 후, 혼합 용액을, 예를 들면, 스팀 스트리핑 등을 행하여 중합 용매를 분리하고, 건조함으로써 얻을 수 있다. 또한, 블록 공중합체(a), (b)의 용액에 대하여 개별적으로 중합 용매를 분리, 건조해서 얻어진 폴리머를 롤 등으로 블랜딩하여 얻을 수도 있다.The block copolymer composition (A) which consists of the block copolymer (a) and (b) which comprises this invention polymerizes styrene using an organolithium compound as a polymerization initiator, for example in an inert hydrocarbon solvent, and then obtains a polymer And butadiene are polymerized, and in some cases, these operations are repeated to obtain two kinds of styrene-butadiene block copolymer polymers (a) and (b) separately and are obtained by mixing. At this time, the molecular weight is adjusted by controlling the amount of the organolithium compound. Mixing method of a composition (A) mixes after completion | finish of a polymerization reaction, adds water, alcohol, an acid, etc., and inactivates an active species, or after completion | finish of a polymerization reaction, separates the solution of a block copolymer (a), (b) After deactivation and mixing, the mixed solution can be obtained by, for example, steam stripping or the like to separate the polymerization solvent and dry it. Moreover, the polymer obtained by separating and drying a polymerization solvent individually with respect to the solution of block copolymer (a) and (b) can also be obtained by blending with a roll etc.
본 발명을 구성하는 블록 공중합체(a) 및 (b)로 이루어지는 블록 공중합체 조성물(A)은, 상기 이외의 방법으로도 얻을 수 있다. 즉, 상기와 동일한 방법으로 (b) 성분을 중합한 후, 중합계 내에 적당한 커플링제를 유기 리튬 화합물에 대하여, 소정량 첨가함으로써 얻어지는 공중합체 생성물을 (a) 성분으로 하여, 동일 반응계 내에서 원하는 조성물을 얻는다. 이 방법을 이용하면, 모노알케닐 방향족 화합물을 주체로 하는 중합체 블록 부분의 분자량 및 분자량 분포가 (a) 성분과 (b) 성분에서 완전히 동일해지므로, 블록 공중합체 조성물의 응집력이 향상되고, 대단히 우수한 점착 성능을 나타낸다.The block copolymer composition (A) which consists of the block copolymer (a) and (b) which comprises this invention can be obtained also by the method of that excepting the above. In other words, after the polymerization of component (b) in the same manner as described above, the copolymer product obtained by adding a predetermined amount of a suitable coupling agent to the organolithium compound in the polymerization system is used as the component (a), and the desired reaction is carried out in the reaction system. Obtain the composition. By using this method, since the molecular weight and molecular weight distribution of the polymer block portion mainly composed of the monoalkenyl aromatic compound are completely the same in the component (a) and the component (b), the cohesive force of the block copolymer composition is improved and greatly Excellent adhesion performance.
또한, 본 발명을 구성하는 블록 공중합체는, 공액 디엔에서 유래하는 불포화 이중 결합의 일부 또는 전부에서 수소 첨가되어 있어도 된다. 이러한 수소화 방법은 특별히 한정되지 않고, 공지된 기술을 이용해서 행해진다.In addition, the block copolymer which comprises this invention may be hydrogenated by one part or all part of the unsaturated double bond derived from conjugated diene. This hydrogenation method is not specifically limited, It uses a well-known technique.
본 발명에서 사용되는 불활성 탄화수소 용매로서는, 부탄, 펜탄, 헥산, 이소펜탄, 헵탄, 옥탄, 이소옥탄 등의 지방족 탄화수소, 시클로펜탄, 메틸시클로펜탄, 시클로헥산, 메틸시클로헥산, 에틸시클로헥산 등의 지환족 탄화수소, 벤젠, 톨루엔, 에틸벤젠, 크실렌 등의 방향족 탄화수소 등의 탄화수소 용매를 사용할 수 있다. 이들은 1종뿐만 아니라 2종 이상을 혼합해서 사용할 수도 있다.Examples of the inert hydrocarbon solvent used in the present invention include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane and isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane. Hydrocarbon solvents, such as aromatic hydrocarbons, such as a hydrocarbon, benzene, toluene, ethylbenzene, and xylene, can be used. These can also be used in mixture of 2 or more types as well as 1 type.
또한, 본 발명에서 사용되는 유기 리튬 화합물로서는, 공지된 화합물, 예를 들면 에틸리튬, 프로필리튬, n-부틸리튬, sec-부틸리튬, tert-부틸리튬, 페닐리튬, 프로페닐리튬, 헥실리튬 등을 들 수 있다. 이 중에서도 n-부틸리튬, sec-부틸리튬이 바람직하다. 유기 리튬 화합물은 1종뿐만 아니라, 2종 이상의 혼합물로서도 이용할 수 있다. 원하는 피크 분자량에 따라서 사용량은 달라진다.Moreover, as an organolithium compound used by this invention, a well-known compound, for example, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, tert- butyl lithium, phenyl lithium, propenyl lithium, hexyl lithium, etc. Can be mentioned. Among these, n-butyllithium and sec-butyllithium are preferable. The organolithium compound can be used not only as one kind but also as a mixture of two or more kinds. The amount used depends on the desired peak molecular weight.
또한, 블록 공중합체(a), (b)에 있어서, 예를 들면 공액 디엔 화합물을 주체로 하는 중합체 블록이 모노알케닐 방향족 화합물과 공액 디엔 화합물의 랜덤 공중합체 블록일 경우, 모노알케닐 방향족 화합물을 중합시킨 후, 모노알케닐 방향족 화합물과 공액 디엔 화합물을 동시에 도입하여 중합시키는 방법이나, 모노알케닐 방향족 화합물과 공액 디엔 화합물의 일부를 동시에 중합시키고, 이어서 공액 디엔 화합물을 추가적으로 첨가하는 방법 등도 이용할 수 있다. 또한, 중합 개시전, 및/또는 중합 반응 중에 극성 화합물을 첨가해서 모노알케닐 방향족 화합물 연쇄 분포를 조정하는 것이 가능하다. 극성 화합물로서는, 예를 들면, 에테르류나 제3급 아민류 등이며, 구체적으로는, 에틸렌글리콜디메틸에테르, 테트라하이드로푸란, α-메톡시테트라하이드로푸란, N,N,N',N'-테트라메틸에틸렌디아민 등으로부터 선택되는 1종 또는 2종 이상의 혼합물이 사용된다. 또한, 알칼리 금속 제3급 알콕시드를 사용할 수도 있다. 알칼리 금속 제3급 알콕시드로서는, 예를 들면 칼륨-t-부톡시드, 칼륨-t-아밀알콕시드, 나트륨아밀알콕시드, 칼륨이소펜틸옥시드 등을 들 수 있다.In the block copolymers (a) and (b), for example, when the polymer block mainly composed of the conjugated diene compound is a random copolymer block of the monoalkenyl aromatic compound and the conjugated diene compound, the monoalkenyl aromatic compound After polymerization, the monoalkenyl aromatic compound and the conjugated diene compound may be introduced and polymerized simultaneously, or the monoalkenyl aromatic compound and a part of the conjugated diene compound may be simultaneously polymerized, and then a conjugated diene compound may be additionally added. Can be. It is also possible to adjust the monoalkenyl aromatic compound chain distribution by adding a polar compound before the start of polymerization and / or during the polymerization reaction. Examples of the polar compound include ethers, tertiary amines, and the like, and specifically, ethylene glycol dimethyl ether, tetrahydrofuran, α-methoxytetrahydrofuran, N, N, N ', N'-tetramethyl One or a mixture of two or more selected from ethylenediamine and the like is used. Moreover, an alkali metal tertiary alkoxide can also be used. As an alkali metal tertiary alkoxide, potassium-t-butoxide, potassium-t-amyl alkoxide, sodium amyl alkoxide, potassium isopentyl oxide, etc. are mentioned, for example.
또한, 블록 공중합체(a), (b) 중의 공액 디엔 화합물의 비닐 결합량을 조정하기 위하여, 예를 들면, 에테르류나 제3급 아민류 등, 구체적으로는, 에틸렌글리콜디메틸에테르, 테트라하이드로푸란, α-메톡시테트라하이드로푸란, N,N,N',N'-테트라메틸에틸렌디아민 등으로부터 선택되는 1종 또는 2종 이상의 혼합물이 사용되지만, 특히 고도의 내열성이 필요할 경우, 비닐 결합량은 20% 미만인 것이 바람직하다.Moreover, in order to adjust the vinyl bond amount of the conjugated diene compound in a block copolymer (a) and (b), For example, ethylene glycol dimethyl ether, tetrahydrofuran, etc., such as ethers and tertiary amines, One or two or more mixtures selected from α-methoxytetrahydrofuran, N, N, N ', N'-tetramethylethylenediamine and the like are used, but the amount of vinyl bonds is 20, especially if high heat resistance is required It is preferably less than%.
본 발명을 구성하는 블록 공중합체(a)가, 블록 공중합체(b)를 커플링 반응시켜서 얻어질 경우, 커플링제로서는, 예를 들면 2작용성 에폭시 화합물, 디메틸디메톡시실란, 디메틸디에톡시실란, 트리메톡시메틸실란, 트리에톡시실란, 테트라메톡시실란, 테트라에톡시실란과 같은 알콕시 규소 화합물, 벤조산메틸, 벤조산에틸과 같은 에스테르 화합물, 디비닐벤젠 등과 같은 비닐알렌류, 디클로로디메틸실란, 페닐메틸디클로로실란과 같은 할로겐화 규소 화합물, 디클로로디메틸주석, 테트라클로로주석과 같은 주석 화합물, 테트라클로로실란과 같은 규소 화합물, 등을 들 수 있다. 이들 중에서도, 감압성 접착제 성능의 관점에서 2작용성 커플링제를 이용하는 것이 바람직하며, 또한, 감압성 접착제 조성물의 가열 변색성의 관점에서, 비할로겐계 커플링제를 이용하는 것이 바람직하다.When the block copolymer (a) which comprises this invention is obtained by coupling-reacting a block copolymer (b), as a coupling agent, for example, a bifunctional epoxy compound, dimethyldimethoxysilane, and dimethyl diethoxysilane , Alkoxy silicon compounds such as trimethoxymethylsilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, ester compounds such as methyl benzoate and ethyl benzoate, vinylenes such as divinylbenzene, dichlorodimethylsilane, And halogenated silicon compounds such as phenylmethyldichlorosilane, tin compounds such as dichlorodimethyltin, and tetrachlorotin, and silicon compounds such as tetrachlorosilane. Among these, it is preferable to use a bifunctional coupling agent from a viewpoint of pressure-sensitive adhesive performance, and it is preferable to use a non-halogen type coupling agent from the viewpoint of the heat discoloration of a pressure-sensitive adhesive composition.
또한, 본 발명을 구성하는 블록 공중합체에 있어서, 상기 커플링제 화합물은 단독으로 사용할 수도 있고, 2종 이상의 혼합물로 사용할 수도 있다.In addition, in the block copolymer which comprises this invention, the said coupling agent compound may be used independently and may be used in mixture of 2 or more types.
본 발명의 감압성 접착제 조성물에 이용할 수 있는 성분(B)으로서는, 얻어지는 점착제 조성물의 용도, 요구 성능에 따라 다양하게 선택된다. 예를 들면, 쿠마론계 수지, 방향족계 탄화수소 수지, 로진계 수지, 테르펜계 수지, 석유 수지, 페놀계 수지, 테르펜-페놀계 수지, 지환족계 탄화수소 수지, 수첨 지환족계 탄화수소 수지, 수첨 테르펜계 수지, 수첨 로진계 수지 등의 공지된 점착 부여제 수지를 들 수 있고, 이들 점착 부여제 수지는 2종 이상의 혼합 사용도 가능하다. 또한, 감압성 접착제 조성물의 내가열 변색성이 강하게 요구될 경우, 불포화부에 수소가 첨가된 점착 부여제 수지가 바람직하다.As a component (B) which can be used for the pressure-sensitive adhesive composition of this invention, it selects variously according to the use of the adhesive composition obtained, and a required performance. For example, coumarone resin, aromatic hydrocarbon resin, rosin resin, terpene resin, petroleum resin, phenol resin, terpene-phenol resin, cycloaliphatic hydrocarbon resin, hydrogenated cycloaliphatic hydrocarbon resin, hydrogenated terpene resin, Known tackifier resins, such as hydrogenated rosin-type resin, are mentioned, These tackifier resin can also use 2 or more types of mixtures. Moreover, when heat-resistant discoloration property of a pressure-sensitive adhesive composition is strongly requested | required, tackifier resin which hydrogen was added to the unsaturated part is preferable.
본 발명에 있어서의 점착 부여성 수지의 배합량은 상기 블록 공중합체 1OO중량부당, 얻어지는 감압성 접착제 조성물의 택 성능의 관점 및 점착력, 유지력 성능의 관점에서, 20∼600중량부, 바람직하게는 50∼400중량부가 사용된다.The compounding quantity of the tackifying resin in this invention is 20-600 weight part per 100 weight part of said block copolymers from a viewpoint of the tack performance of the pressure-sensitive adhesive composition obtained, and a viewpoint of adhesive force and a holding force performance, Preferably it is 50- 400 parts by weight is used.
그리고, 본 발명의 조성물에서는, 연화제((C) 성분)를 사용할 수 있다. 연화제의 종류는 제한되지 않고, 공지된 파라핀계나 나프텐계 프로세스 오일 및 이들의 혼합 오일을 사용할 수 있다. 감압성 접착제 조성물의 색조가 중요할 경우, 파라핀계 오일이 보다 바람직하다.And in the composition of this invention, a softener ((C) component) can be used. The type of softener is not limited, and known paraffinic or naphthenic process oils and mixed oils thereof can be used. When the color tone of the pressure-sensitive adhesive composition is important, paraffinic oils are more preferred.
그 사용량은, 상기 블록 공중합체 100중량부당, 얻어지는 감압성 접착제 조성물의 유지력 성능이나 오일 블리딩 등의 외관성의 관점에서, 0∼300중량부의 범위 내에서 사용된다.The usage-amount is used in the range of 0-300 weight part per 100 weight part of said block copolymers from a viewpoint of external appearance, such as the holding force performance of the pressure-sensitive adhesive composition obtained, oil bleeding, and the like.
본 발명의 점착제 조성물에 있어서, 필요에 의해 산화 방지제를 첨가할 수 있고, 열안정성을 더욱 향상시키거나, 내열변색성을 향상시킬 수도 있다. 산화 방지제로서는, 예를 들면, 2,4-비스(n-옥틸티오메틸)-O-크레졸, 2,4-비스(n-도데실 티오메틸)-O-크레졸, 2,4-비스(페닐티오메틸)-3-메틸-6-tert-부틸페놀, n-옥타데실3-(3',5'디-tert-부틸-4'-히드록시페닐)프로피오네이트, 2,2'-메틸렌비스(4-에틸-6-tert-부틸페놀), 테트라키스-[메틸렌-3-(3',5'-디-tert-부틸-4'-히드록시페닐)프로피오네이트]-메탄, 1,3,5-트리메틸-2,4,6-트리스(3,5-디-tert-부틸-4-히드록시벤질)벤젠, 2,6-디-tert-부틸-4-메틸페놀, 2,6-디-tert-부틸-4-에틸페놀, 2-tert-부틸-6-(3-tert-부틸-2-히드록시-5-메틸벤질)-4-메틸페닐아크릴레이트, 2,4-디-tert-아밀-6-[1-(3,5-디-tert-아밀-2-히드록시페닐)에틸]페닐아크릴레이트, 2-[1-(2-히드록시-3,5-디-tert-펜틸페닐)-에틸]-4,6-디-tert-펜틸페닐아크릴레이트, 3,9-비스[2-[3-(3-tert-부틸-4-히드록시-5-메틸페닐)-[프로피오닐옥시]-1,1-디메틸에틸]-2,4,8,10-테트라옥사스피로[5,5]운데칸 등의 힌더드(hindered) 페놀계 화합물, 펜타에리스톨테트라키스-(β-라우릴-티오-프로피오네이트), 디라우릴-3,3'-티오디프로피오네이트, 디미리스틸-3,3'-티오디프로피오네이트, 디스테아릴-3,3'-티오디프로피오네이트 등의 이온계 화합물, 트리스(노닐페닐)포스파이트, 사이클릭네오펜타테트라일비스(옥타데실포스파이트), 트리스(2,4-디-tert-부틸페닐)포스파이트 등의 인계 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합해서 사용할 수 있다. 이들의 첨가량은 용도에 따라 달라지지만, 바람직하게는 점착제 조성물 100중량부에 대하여 5중량부 이하이다.In the adhesive composition of this invention, antioxidant can be added as needed, heat stability can be improved further, or heat discoloration resistance can also be improved. Examples of the antioxidants include 2,4-bis (n-octylthiomethyl) -O-cresol, 2,4-bis (n-dodecyl thiomethyl) -O-cresol and 2,4-bis (phenyl Thiomethyl) -3-methyl-6-tert-butylphenol, n-octadecyl3- (3 ', 5'di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-methylene Bis (4-ethyl-6-tert-butylphenol), tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] -methane, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-di -tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl] phenylacrylate, 2- [1- (2-hydroxy-3,5-di- tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenylacrylate, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl)- [Propionyloxy] -1,1-dimethylethyl] -2 Hindered phenolic compounds such as, 4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis- (β-lauryl-thio-propionate), dilauryl- Ionic compounds such as 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and tris (nonylphenyl Phosphorus compounds, such as a phosphite, a cyclic neopentate tetrayl bis (octadecyl phosphite), and a tris (2, 4-di-tert- butylphenyl) phosphite, etc. are mentioned. These can be used individually or in mixture of 2 or more types. Although these addition amount changes with a use, Preferably it is 5 weight part or less with respect to 100 weight part of adhesive compositions.
또한, 본 발명의 점착제 조성물에서는 광안정제를 사용할 수도 있다. 광안정제로서는, 2-(2'-히드록시-5'-메틸페닐)벤조트리아졸, 2-(2'-히드록시-5'-tert-옥틸페닐)벤조트리아졸, 2-(2'-히드록시-3',5'-디-tert-부틸페닐)벤조트리아졸, 2-(2'-히드록시-3',5'-디-tert-부틸페닐)-5-클로로벤조트리아졸, 2-(2'-히드록시-3'-tert-부틸-5'-메틸페닐)-5-클로로벤조트리아졸 등의 벤조 트리아졸계 화합물이나, 비스(2,2,6,6-테트라메틸-4-피페리딜)세바케이트, 숙신산디메틸-1-(2-히드록시에틸)-4-히드록시-2,2,6,6-테트라메틸피페리딘 중축합물, 폴리[(6-(1,1,3,3-테트라메틸부틸)이미노-1,3,5-트리아진-2,4-디일)[2,2,6,6-테트라메틸-4-피페리딜]이미노]헥사메틸렌[[2,2,6,6-테트라메틸-4-피페리딜]이미노]] 등의 힌더드 아민계 화합물, 2-히드록시4-메톡시벤조페논 등의 벤조페논계 화합물 등을 들 수 있다.Moreover, in the adhesive composition of this invention, a light stabilizer can also be used. Examples of the light stabilizer include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole and 2- (2'-hydride. Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2 Benzotriazole compounds such as-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and bis (2,2,6,6-tetramethyl-4- Piperidyl) sebacate, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [(6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) [2,2,6,6-tetramethyl-4-piperidyl] imino] hexamethylene Hindered amine compounds, such as [[2,2,6,6-tetramethyl-4-piperidyl] imino]], Benzophenone series compounds, such as 2-hydroxy 4-methoxy benzophenone, etc. are mentioned. Can be.
벤조 트리아졸계 화합물이나 힌더드 아민계 화합물, 벤조페논계 화합물 등을 본 발명의 조성물과 조합함으로써, 내광성을 더 개선할 수 있다.By combining a benzotriazole compound, a hindered amine compound, a benzophenone compound and the like with the composition of the present invention, light resistance can be further improved.
상기 안정제 이외에, 본 발명의 점착제 조성물에는, 필요에 따라, 벤가라, 이산화티탄 등의 안료, 파라핀 왁스, 마이크로클리스탈 왁스, 저분자량 폴리에틸렌 왁스 등의 왁스류, 무정형 폴리올레핀, 에틸렌에틸아크릴레이트 공중합체 등의 폴리올레핀계 또는 저분자량 비닐 방향족계 열가소성 수지, 천연 고무, 폴리이소프렌 고무, 폴리부타디엔 고무, 스티렌부타디엔 고무, 에틸렌-프로필렌 고무, 클로로프렌 고무, 아크릴 고무, 이소프렌-이소부틸렌 고무, 폴리펜테나머 고무, 본 발명 이외의 스틸렌-부타디엔계 블록 공중합체, 스틸렌-이소프렌계 블록 공중합체, 수소화 스틸렌-부타디엔계 블록 공중합체, 수소화 스틸렌-이소프렌계 블록 공중합체 등의 합성 고무를 첨가할 수도 있다.In addition to the stabilizer, the pressure-sensitive adhesive composition of the present invention, if necessary, pigments such as bengar and titanium dioxide, paraffin wax, microcrystalline wax, waxes such as low molecular weight polyethylene wax, amorphous polyolefins, and ethylene ethyl acrylate copolymers. Polyolefin-based or low molecular weight vinyl aromatic thermoplastic resins, natural rubber, polyisoprene rubber, polybutadiene rubber, styrenebutadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypenteneamer Synthetic rubbers, such as rubber, a styrene-butadiene block copolymer other than this invention, a styrene-isoprene-type block copolymer, a hydrogenated styrene-butadiene type block copolymer, and a hydrogenated styrene-isoprene type block copolymer, can also be added.
본 발명의 점착제 조성물은, 공지된 혼합기, 반죽기 등으로 가열하에서 균일혼합하는 방법으로 제조된다.The adhesive composition of this invention is manufactured by the method of homogeneous mixing under heating with a well-known mixer, kneader, etc.
이하, 실시예 및 비교예를 참조하여 본 발명을 더욱 상세하게 설명하지만, 본 발명이 이들 실시예에 한정되는 것은 아니다. 한편, 각종 측정은 하기 방법을 사용했다.Hereinafter, although this invention is demonstrated in detail with reference to an Example and a comparative example, this invention is not limited to these Examples. In addition, the various methods used the following method.
(A) 블록 공중합체의 분석(A) Analysis of Block Copolymers
A-1) 블록 공중합체의 전체 스티렌 함유량:A-1) Total Styrene Content of Block Copolymer:
자외선 분광 광도계(히타치 UV200)를 이용하고, 262nm의 흡수 강도로부터 산출했다.It calculated from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).
A-2) 부타디엔부의 비닐 결합 함유량:A-2) Vinyl Bond Content in Butadiene Part:
적외선 분광 광도계(파킨엘머 제품 모델 1710)를 이용해서 측정하고, 햄톤법(「Analytical Chem., 21, 943('43)」에 기재)에 의해 측정했다.It measured using the infrared spectrophotometer (Model Parkin Elmer Model 1710), and measured by the Hampton method (described in "Analytical Chem., 21, 943 ('43)").
A-3) 블록 공중합체의 피크 분자량 및 블록 공중합체(a)와 블록 공중합체(b)의 조성비:A-3) Peak molecular weight of the block copolymer and the composition ratio of the block copolymer (a) and the block copolymer (b):
GPC(장치는 워터스사 제품, 컬럼은 폴리머연구소사 제품인 MINIMIX를 3개 장착했다. 용매로는 테트라하이드로푸란을 이용하고, 측정 조건은, 온도 35℃, 유속 0.4m1/분, 시료 농도 0.1중량%, 주입량 40㎕임)의 크로마토그램에 의하여, 피크 분자량 및 블록 공중합체의 조성비를 구했다. 한편, 피크 분자량은, 아래의 표준 폴리스티렌(오쿠즈사 제품. 1.54×106, 4.1×105, 1.10×105, 3.5×104, 8.5×103, 1.8×103) 검량선으로부터의 환산값이다.GPC (equipment was equipped with three MINIMIX manufactured by Waters Co., Ltd. and Polymer Lab. Co., Ltd.) using tetrahydrofuran as a solvent, and measurement conditions were a temperature of 35 DEG C, a flow rate of 0.4 m1 / min, and a sample concentration of 0.1 wt%. The peak molecular weight and the composition ratio of a block copolymer were calculated | required by the chromatogram of 40 microliters of injection amount. On the other hand, the peak molecular weight is converted from the following standard polystyrene (Okuzu Co., Ltd. product 1.54 × 10 6 , 4.1 × 10 5 , 1.10 × 10 5 , 3.5 × 10 4 , 8.5 × 10 3 , 1.8 × 10 3 ) calibration curve to be.
A-4) 스티렌 블록 중합체의 피크 분자량 및 Mw/Mn:A-4) Peak Molecular Weight and Mw / Mn of Styrene Block Polymer:
4산화오스뮴과 t-부틸하이드로퍼옥시드에 의한 산화 분해법["저널·오브·폴리머·사이언스" 제1권, 제429페이지(1946년)에 기재]을 따라서 얻어진 스티렌 중합체 블록을 GPC(장치는 워터스 제품이며, 컬럼은 쇼와덴코사 제품인 Shodex-K803, K802, K801을 장착했다. 용매로는 클로로포름을 이용하고, 측정 조건은, 온도 35℃, 유속 1.0m1/분, 시료 농도 0.05중량%, 주입량 100㎕임)를 이용해서 측정했다.The styrene polymer block obtained by oxidative decomposition using osmium tetraoxide and t-butylhydroperoxide [described in the Journal of Polymer Science, Vol. 1, p. Shodex-K803, K802, and K801, manufactured by Showa Denko Co., Ltd., were used as water solvents, and chloroform was used as a solvent, and measurement conditions were a temperature of 35 ° C., a flow rate of 1.0 m 1 / min, a sample concentration of 0.05 wt%, Injection amount of 100 µl).
A-5) 15% 톨루엔 용액 점도:A-5) 15% Toluene Solution Viscosity:
15% 톨루엔 용액 점도는, 캐논-펜스케 점도관을 이용하고, 25℃의 온도로 유지된 항온조에서 측정했다.The 15% toluene solution viscosity was measured in the thermostat maintained at the temperature of 25 degreeC using the Canon-Penske viscosity tube.
A-6) 내블록킹성:A-6) Blocking Resistance:
내블록킹성은, 직경 75mm의 염화비닐 파이프에 에틸렌비스스테아릴아미드를 1000ppm 첨가한 폴리머 조성물을 300g 충전하고, 3kg의 하중을 적용하고, 50℃에서 24시간 방치 후, 하중을 제거해서 1시간 실온 정치 후 염화비닐 파이프를 제거한다. 이어서, 상기 원통형 샘플을 TENSlLON-UTM-III형 인장 시험기(동양측기사 제품)를 이용하여, 500mm/min의 속도로 압축하고, 파괴될 때의 하중을 측정한다.Blocking resistance, 300 g of a polymer composition to which 1000 ppm of ethylene bis stearylamide was added to a 75 mm diameter vinyl chloride pipe was applied, and a load of 3 kg was applied, and after standing at 50 ° C. for 24 hours, the load was removed and left at room temperature for 1 hour. After removing the vinyl chloride pipe. The cylindrical sample is then compressed using a TENSLON-UTM-III type tensile tester (manufactured by Dongyang Technological Co., Ltd.) at a rate of 500 mm / min and the load at breakage is measured.
(B) 감압성 접착제 조성물의 물성의 측정(B) Measurement of physical properties of pressure-sensitive adhesive composition
감압성 접착제 조성물의 물성 측정은 상기 조성물을 용융 상태에서 꺼내고, 어플리케이터로 폴리에스테르 필름에 두께 50μm로 코팅하여, 점착 테이프 샘플을 제조하여, 점성, 점착력, 유지력을 아래의 방법으로 측정했다.The physical property measurement of the pressure-sensitive adhesive composition was taken out of the molten state, coated on a polyester film with a thickness of 50 μm with an applicator to prepare an adhesive tape sample, and the viscosity, adhesive force, and holding force were measured by the following method.
B-1) 루프 택:B-1) Loop Tag:
길이 250mm×폭 15mm의 루프형 시료를 이용하고, PE판에 대한 접촉 면적: 15mm×50mm, 접착 시간: 3sec, 접착 및 필링 속도: 500mm/min로 측정했다.Using a loop-shaped sample having a length of 250 mm x 15 mm, the contact area with respect to the PE plate was measured at 15 mm x 50 mm, the adhesion time: 3 sec, and the adhesion and peeling speed: 500 mm / min.
B-2) 점착력:B-2) Adhesion:
폭 25mm의 시료를 폴리에틸렌 판에 접착시키고, 필링 속도 300mm/min로 180℃ 박리력을 측정했다.A sample having a width of 25 mm was adhered to a polyethylene plate and 180 ° C peel force was measured at a peeling speed of 300 mm / min.
B-3) 유지력:B-3) Holding Force:
유지력은, 스테인리스 강판 및 PE 판에 25mm×25mm의 면적이 접하도록 점착테이프를 붙이고, 60℃에서 1kg의 하중을 부여해서 점착 테이프가 어긋나서 떨어질 때까지의 시간을 측정했다.The holding force was affixed on a stainless steel sheet and a PE plate so that an area of 25 mm x 25 mm could be contacted, and the time until the adhesive tape shifted and fell was given by applying a load of 1 kg at 60 degreeC.
B-4) 점착제 조성물의 내열변색성:B-4) Heat discoloration resistance of the pressure-sensitive adhesive composition:
점착제 조성물의 내열변색성은, 180℃의 기어 오븐에 넣어서, 표 1 나타낸 시간 동안 가열한 후의 색조를 조사했다.The heat discoloration resistance of the adhesive composition was put into a gear oven at 180 ° C, and the color tone after heating for the time shown in Table 1 was examined.
B-5) 점착제 조성물의 용융 점도:B-5) Melt Viscosity of Adhesive Composition:
점착제 조성물의 용융 점도는, 표 1에 나타낸 온도에서 브룩 필드형 점도계에 의해 측정했다.Melt viscosity of the pressure-sensitive adhesive composition was measured by a Brookfield viscometer at the temperature shown in Table 1.
B-6) 점착제 조성물의 내열성(용융 점도 변화):B-6) Heat resistance of the pressure-sensitive adhesive composition (melt viscosity change):
점착제 조성물을 180℃의 기어 오븐에 표 1에 나타낸 시간 동안 넣은 후, 용융 점도를 측정했다.After putting the adhesive composition in the gear oven at 180 degreeC for the time shown in Table 1, melt viscosity was measured.
실시예Example 1 One
본 발명의 실시예에서 사용한 블록 공중합체는, 아래와 같이 제조했다.The block copolymer used in the Example of this invention was manufactured as follows.
재킷과 교반기가 부착된 40L의 스테인리스강 재질의 반응기를 충분히 질소 치환한 후, 시클로헥산 17,600g, 테트라하이드로푸란 4.8g, 스티렌 1470g을 주입하고, 재킷에 온수를 통과시켜서 내용물을 약 55℃로 설정했다. 이어서, n-부틸리튬시클로헥산 용액(순 함량 5.5g)을 첨가하여, 스티렌의 중합을 개시했다. 스티렌이 거의 완전히 중합된 후 3분 경과 후에, 부타디엔(1,3-부타디엔) 1730g을 첨가하여 중합을 계속하고, 부타디엔이 거의 완전히 중합되어서 최고 온도 약 90℃에 도달한 후 4분 경과 후에, 커플링제로서 비스페놀류의 디글리시딜에테르 화합물을 n-부틸리튬에 대하여 0.33당량 첨가하여, 커플링 반응시켰다. 스티렌을 주입한 직후부터 이때까지 교반기로 계 내부를 연속적으로 계속 교반했다.After fully nitrogen-substituting a 40L stainless steel reactor with a jacket and a stirrer, 17,600 g of cyclohexane, 4.8 g of tetrahydrofuran, and 1470 g of styrene were injected, and the contents were set to about 55 ° C. by passing hot water through the jacket. did. Subsequently, n-butyllithium cyclohexane solution (5.5 g of net content) was added to start polymerization of styrene. Three minutes after the styrene was almost completely polymerized, 1730 g of butadiene (1,3-butadiene) was added to continue the polymerization, and after four minutes after the butadiene was almost completely polymerized and reached the maximum temperature of about 90 ° C., the couple was As a ring agent, 0.33 equivalent of diglycidyl ether compound of bisphenols was added with respect to n-butyllithium, and the coupling reaction was carried out. From immediately after injecting styrene, the inside of the system was continuously stirred with a stirrer.
얻어진 블록 공중합체 용액을 꺼내고, 물 20g을 첨가, 교반한 후, n-옥타데실-3-(3',5'디-tert-부틸-4'-히드록시페닐)프로피오네이트를 3.2g, 2,4-비스(n-옥틸티오메틸)-O-크레졸을 1.0g 첨가하고, 얻어진 상기 용액을 스팀 스트리핑함으로써, 용매를 제거하여 함수 크럼(crumb)을 얻었다. 이어서, 열 롤에 의해 탈수 건조시켜서, 블록 공중합체 조성물 샘플을 얻었다.The obtained block copolymer solution was taken out, and 20 g of water was added and stirred, followed by 3.2 g of n-octadecyl-3- (3 ', 5'di-tert-butyl-4'-hydroxyphenyl) propionate. 1.0 g of 2,4-bis (n-octylthiomethyl) -O-cresol was added, and the obtained solution was steam stripped to remove the solvent to obtain a hydrous crumb. Subsequently, it dehydrated and dried by the heat roll, and the block copolymer composition sample was obtained.
이렇게 얻어진 블록 공중합체 조성물 10Og을, 점착 부여성 수지로서, 지환족 포화 탄화수소 수지인 아르콘 M100(아라카와화학사 제품: 상품명)을 250g, 연화제로서 다이아나 프로세스 오일 PW-90(이데미쓰코산사 제품: 상품명)을 60g, 열안정제로서 서밀라이저 GM(스미토모화학사 제품: 상품명)을 1g 배합하고, 180℃×2시간, 1리터의 교반기 부착 용기로 용융 혼련하여 핫 멜트형 감압성 접착제 조성물을 얻었다.100 g of the block copolymer composition thus obtained was 250 g of Arcon M100 (manufactured by Arakawa Chemical Co., Ltd.), which is an alicyclic saturated hydrocarbon resin, as a tackifier resin, and Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) as an emollient. 60 g and 1 g of thermolyzer GM (product of Sumitomo Chemical Co., Ltd.) were mix | blended as a heat stabilizer, melt-kneading with the container with a stirrer of 180 degreeC x 2 hours, and the hot melt type pressure-sensitive adhesive composition was obtained.
실시예Example 2 2
스티렌, 부타디엔(1,3-부타디엔) 유입량, n-부틸리튬시클로헥산 용액의 첨가량을 변경한 것 이외에는 실시예 1과 동일한 방법으로 중합해서 얻은 블록 공중합체 폴리머 용액에, 부타디엔이 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 디메톡시디메틸실란을 n-부틸리튬에 대하여 0.28당량 첨가하여, 커플링 반응시켰다. 이때, 교반기에 의해 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조시키고, 블록 공중합체 조성물을 얻어서, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Butadiene was almost completely polymerized in the block copolymer polymer solution obtained by polymerization in the same manner as in Example 1 except that the amount of styrene, butadiene (1,3-butadiene) inflow and the amount of n-butyllithium cyclohexane solution were changed. After 4 minutes of reaching the temperature, 0.28 equivalents of dimethoxydimethylsilane was added to the n-butyllithium as a coupling agent to cause a coupling reaction. At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
실시예Example 3 3
재킷과 교반기가 부착된 40L의 스테인리스강 재질 반응기를 충분히 질소 치환한 후, 시클로헥산 17,600g, 테트라하이드로푸란 4.8g, 스티렌 685g을 넣고, 재킷에 온수를 통과시켜서 내용물을 약 55℃로 설정했다. 이어서, n-부틸리튬시클로헥산 용액(순 함량 2.9g)을 첨가하여, 스티렌의 중합을 개시했다. 스티렌이 거의 완전히 중합된 후 3분 경과 후에, 부타디엔(1,3-부타디엔) 1830g을 첨가하여 중합을 계속하고, 부타디엔이 거의 완전히 중합된 후 4분 경과 후에, 스티렌 685g을 첨가하여 완전히 중합을 종료시켜서, 블록 공중합체(a)를 얻었다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체(a) 용액을 꺼내고, 물 20g을 첨가, 교반 후, n-옥타데실-3-(3',5'디-tert-부틸-4'-히드록시페닐)프로피오네이트를 3.2g, 2,4-비스(n-옥틸티오메틸)-O-크레졸을 1.0g 첨가했다. 또한, 재킷과 교반기가 부착된 40L의 스테인리스강 재질의 반응기를 충분히 질소 치환한 후, 시 클로헥산 17,600g, 테트라하이드로푸란 4.8g, 스티렌 1370g을 넣고, 재킷에 온수를 통과시켜서 내용물을 약 55℃로 설정했다. 이어서, n-부틸리튬시클로헥산 용액(순 함량 5.8g)을 첨가하여, 스티렌의 중합을 개시했다. 스티렌이 거의 완전히 중합된 후 3분 경과 후에, 부타디엔(1,3-부타디엔) 1830g을 첨가하여 완전히 중합 종료시켜서, 블록 공중합체(b)를 얻었다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체(b) 용액을 꺼내고, 물 20g을 첨가, 교반 후, n-옥타데실-3-(3',5'디-tert-부틸-4'-히드록시페닐)프로피오네이트를 3.2g, 2,4-비스(n-옥틸티오메틸)-O-크레졸을 1.0g 첨가했다.After fully nitrogen-substituting the 40 L stainless steel reactor with a jacket and a stirrer, 17,600 g of cyclohexane, 4.8 g of tetrahydrofuran, and 685 g of styrene were added, and the contents were set to about 55 degreeC by passing hot water through a jacket. Next, n-butyllithium cyclohexane solution (net content of 2.9 g) was added to initiate polymerization of styrene. Three minutes after the styrene was almost completely polymerized, 1830 g of butadiene (1,3-butadiene) was added to continue the polymerization, and 4 minutes after the butadiene was almost completely polymerized, 685 g of styrene was added to complete the polymerization completely. To obtain a block copolymer (a). At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer (a) solution was taken out, and 20 g of water was added and stirred, followed by 3.2 n-octadecyl-3- (3 ', 5'di-tert-butyl-4'-hydroxyphenyl) propionate. 1.0 g of g and 2,4-bis (n-octylthiomethyl) -O-cresol were added. In addition, after fully nitrogen-substituting the reactor of 40L stainless steel with a jacket and a stirrer sufficiently, 17,600 g of cyclohexane, 4.8 g of tetrahydrofuran, and 1370 g of styrene were added thereto, and the contents were passed through the jacket by passing hot water. Was set to. Next, n-butyllithium cyclohexane solution (net content of 5.8 g) was added to start polymerization of styrene. Three minutes after the styrene was almost completely polymerized, 1830 g of butadiene (1,3-butadiene) was added to complete polymerization, thereby obtaining a block copolymer (b). At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer (b) solution was taken out, and 20 g of water was added thereto and stirred, followed by 3.2 n-octadecyl-3- (3 ', 5'di-tert-butyl-4'-hydroxyphenyl) propionate. 1.0 g of g and 2,4-bis (n-octylthiomethyl) -O-cresol were added.
이어서, 블록 공중합체(a) 용액과 블록 공중합체 용액(b)을 33/67로 혼합했다. 얻어진 블록 공중합체 조성물 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조시키고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Subsequently, the block copolymer (a) solution and the block copolymer solution (b) were mixed at 33/67. The obtained block copolymer composition solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
비교예Comparative example 1 One
스티렌, 부타디엔(1,3-부타디엔) 유입량, n-부틸리튬시클로헥산 용액의 첨가량을 변경한 것 이외에는 실시예 1과 동일한 방법으로 중합해서 얻은 블록 공중합체 폴리머 용액에, 부타디엔이 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 디메톡시디메틸실란을 n-부틸리튬에 대하여 0.35당량 첨가하여, 커플링 반응시켰다. 스티렌을 주입한 직후부터 이때까지, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Butadiene was almost completely polymerized in the block copolymer polymer solution obtained by polymerization in the same manner as in Example 1 except that the amount of styrene, butadiene (1,3-butadiene) inflow and the amount of n-butyllithium cyclohexane solution were changed. After 4 minutes of reaching the temperature, 0.35 equivalents of dimethoxydimethylsilane was added as n-butyllithium as a coupling agent to cause a coupling reaction. From immediately after injecting styrene to this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
비교예Comparative example 2 2
스티렌, 부타디엔(1,3-부타디엔) 유입량, n-부틸리튬시클로헥산 용액의 첨가량을 변경한 것 이외에는 실시예 1과 동일한 방법으로 중합해서 얻은 블록 공중합체 폴리머 용액에, 부타디엔이 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 비스페놀류의 디글리시딜에테르 화합물을 n-부틸리튬에 대하여 0.64당량 첨가하여, 커플링 반응시켰다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Butadiene was almost completely polymerized in the block copolymer polymer solution obtained by polymerization in the same manner as in Example 1 except that the amount of styrene, butadiene (1,3-butadiene) inflow and the amount of n-butyllithium cyclohexane solution were changed. After 4 minutes of reaching the temperature, 0.64 equivalents of the diglycidyl ether compound of bisphenols was added to the n-butyllithium as a coupling agent to cause a coupling reaction. At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
비교예Comparative example 3 3
재킷과 교반기가 부착된 40L의 스테인리스강 재질의 반응기를 충분히 질소 치환한 후, 시클로헥산 17,600g, 테트라하이드로푸란 4.8g, 스티렌 970g을 넣고, 재킷에 온수를 통과시켜서 내용물을 약 55℃로 설정했다. 이어서, n-부틸리튬시클로헥산 용액(순 함량 6.7g)을 첨가하여, 스티렌의 중합을 개시했다. 스티렌이 거의 완전히 중합된 후 3분 경과 후에, 부타디엔(1,3-부타디엔) 1890g과 스티렌 240g을 첨가하여 중합을 계속하고, 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 디메톡시디메틸실란을 n-부틸리튬에 대하여 0.27당량 첨가하여, 커플링 반응시켰다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블 록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.After fully nitrogen-substituting the reactor of 40L stainless steel with a jacket and a stirrer sufficiently, 17,600 g of cyclohexane, 4.8 g of tetrahydrofuran, and 970 g of styrene were added, and the contents were set to about 55 degreeC by passing hot water through a jacket. . Subsequently, n-butyllithium cyclohexane solution (net content of 6.7 g) was added to initiate polymerization of styrene. 3 minutes after the styrene was almost completely polymerized, 1890 g of butadiene (1,3-butadiene) and 240 g of styrene were added to continue the polymerization, and after 4 minutes after being almost completely polymerized and reaching the maximum temperature, as a coupling agent, 0.27 equivalent of dimethoxydimethylsilane was added with respect to n-butyllithium, and the coupling reaction was carried out. At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
비교예Comparative example 4 4
스티렌, 부타디엔(1,3-부타디엔) 유입량, n-부틸리튬시클로헥산 용액의 첨가량을 병경한 것 이외에는 실시예 1과 동일한 방법으로 중합하여 얻어진 블록 공중합체 폴리머 용액에, 부타디엔이 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 비스페놀류의 디글리시딜에테르 화합물을 n-부틸리튬에 대하여 0.23당량 첨가하여, 커플링 반응시켰다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Butadiene was almost completely polymerized in the block copolymer polymer solution obtained by polymerization in the same manner as in Example 1, except that the amount of styrene, butadiene (1,3-butadiene) inflow and the amount of n-butyllithium cyclohexane solution were added. After 4 minutes of reaching the temperature, 0.23 equivalents of a diglycidyl ether compound of bisphenols was added to the n-butyllithium as a coupling agent to cause a coupling reaction. At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
비교예Comparative example 5 5
재킷과 교반기가 부착된 40L의 스테인리스강 재질의 반응기를 충분히 질소 치환한 후, 시클로헥산 17,600g, 테트라하이드로푸란 4.8g, N,N,N',N'-테트라메틸 에틸렌디아민 1.66g, 스티렌 1340g을 넣고, 재킷에 온수를 통과시켜서 내용물을 약 55℃로 설정했다. 이어서, n-부틸리튬시클로헥산 용액(순 함량 5.1g)을 첨가하여, 스티렌의 중합을 개시했다. 스티렌이 거의 완전히 중합된 후 3분 경과 후에, 부타디엔(1,3-부타디엔) 1860g을 첨가하여 중합을 계속하고, 부타디엔이 거의 완전히 중합되어 최고 온도 약 90℃에 도달한 후 4분 경과 후에, 커플링제로서 비스페놀류의 디글리시딜에테르 화합물을 n-부틸리튬에 대하여 0.33당량 첨가하여, 커플링 반 응시켰다. 스티렌을 주입한 직후부터 이때까지, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.After fully nitrogen-substituting a 40 L stainless steel reactor with a jacket and a stirrer, 17,600 g of cyclohexane, 4.8 g of tetrahydrofuran, 1.66 g of N, N, N ', N'-tetramethyl ethylenediamine, 1340 g of styrene Was put, and the contents were set to about 55 ° C. by passing hot water through the jacket. Next, n-butyllithium cyclohexane solution (net content of 5.1 g) was added to initiate polymerization of styrene. Three minutes after the styrene was nearly fully polymerized, 1860 g of butadiene (1,3-butadiene) was added to continue the polymerization, and after four minutes after the butadiene was almost completely polymerized and reached the maximum temperature of about 90 ° C., the couple was As a ring agent, 0.33 equivalent of diglycidyl ether compound of bisphenol was added with respect to n-butyllithium, and coupling reaction was carried out. From immediately after injecting styrene to this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
참고예Reference Example
스티렌, 부타디엔(1,3-부타디엔) 유입량, n-부틸리튬시클로헥산 용액의 첨가량을 변경한 것 이외에는 실시예 1과 동일한 방법으로 중합하여 얻어진 블록 공중합체 폴리머 용액에, 부타디엔이 거의 완전히 중합되어 최고 온도에 도달한 후 4분 경과 후에, 커플링제로서 디메틸디클로로실란을 n-부틸리튬에 대하여 0.4당량 첨가하여, 커플링 반응시켰다. 이때, 교반기로 계 내부를 연속적으로 교반했다. 얻어진 블록 공중합체 용액을 실시예 1과 동일한 방법으로, 용매 제거, 건조하고, 블록 공중합체 조성물을 얻고, 실시예 1과 동일하게 배합하여, 핫 멜트형 감압성 접착제 조성물을 얻었다.Butadiene was almost completely polymerized in the block copolymer polymer solution obtained by polymerization in the same manner as in Example 1 except that the amount of styrene, butadiene (1,3-butadiene) inflow and the amount of n-butyllithium cyclohexane solution were changed. 4 minutes after reaching the temperature, 0.4 equivalent of dimethyldichlorosilane was added to n-butyllithium as a coupling agent, and the coupling reaction was carried out. At this time, the inside of the system was continuously stirred with a stirrer. The obtained block copolymer solution was removed and dried in the same manner as in Example 1 to obtain a block copolymer composition, and blended in the same manner as in Example 1 to obtain a hot melt pressure-sensitive adhesive composition.
얻어진 각 블록 공중합체 조성물의 구조 및 이들이 배합된 감압성 접착제 조성물의 물성을 표 1에 나타냈다. 본 발명에서 규정한 특정 구조를 가지는 취급성이 우수한 블록 공중합체 조성물을 이용함에 따라, 용융 점도가 낮고 저온 가공성이 우수하고, 동시에 감압성 접착제 성능, 특히 유지력과의 밸런스가 우수하고, 또한 내열성도 지극히 우수한 감압성 접착제 조성물이 얻어짐을 알 수 있다.The structure of each obtained block copolymer composition and the physical property of the pressure-sensitive adhesive composition in which these were mix | blended are shown in Table 1. By using the block copolymer composition excellent in handleability which has the specific structure prescribed | regulated by this invention, it is low in melt viscosity, excellent in low temperature workability, and at the same time excellent in the balance with pressure-sensitive adhesive performance, especially holding force, and also heat resistance It can be seen that an extremely excellent pressure-sensitive adhesive composition is obtained.
[표 1]TABLE 1
*1. F.F.: 내블록킹성 측정시, 압축하면 하중없이 파괴됨.*One. F.F .: Determination of blocking resistance results in compression failure.
*2. 에폭시 커플링제:*2. Epoxy Coupling Agents:
비스페놀류의 디글리시딜에테르 화합물(n0체 98% 이상)Diglycidyl ether compound of bisphenol (more than 98% of n0 bodies)
하기 구조식의 1과 2를 1:1로 혼합한 것1 and 2 of the following structural formula mixed 1: 1
본 발명을 상세히, 또한 특정한 실시예를 참조하여 설명했지만, 본 발명의 기술 사상과 범위를 벗어나지 않으면서 여러 가지 변경이나 수정이 가능함을, 당업자라면 명확히 알 수 있을 것이다.While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.
본 출원은, 2003년 2월 7일 출원된 일본 특허 출원(특원 2003-030484)에 기초하는 것이며, 원용에 의해 그 내용은 본 명세서에 포함된다.This application is based on the JP Patent application (patent application 2003-030484) of an application on February 7, 2003, The content is integrated in this specification by reference.
본 발명에 의하면, 종래의 감압성 접착제 조성물과 관련된 문제를 해결할 수 있으며, 특히, 저온 가공이 용이하며, 외관, 감압성 접착제 성능, 내열성이 지극히 우수한 감압성 접착제 조성물을 제공할 수 있다.According to the present invention, it is possible to solve the problems associated with the conventional pressure-sensitive adhesive composition, and in particular, it is possible to provide a pressure-sensitive adhesive composition having easy low-temperature processing, and extremely excellent in appearance, pressure-sensitive adhesive performance, and heat resistance.
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2004/011255 WO2006013631A1 (en) | 2004-08-05 | 2004-08-05 | Pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20070026854A true KR20070026854A (en) | 2007-03-08 |
| KR100874488B1 KR100874488B1 (en) | 2008-12-18 |
Family
ID=35786932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020077001768A KR100874488B1 (en) | 2004-08-05 | 2004-08-05 | Pressure sensitive adhesive composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8039553B2 (en) |
| EP (1) | EP1775332B1 (en) |
| KR (1) | KR100874488B1 (en) |
| CN (1) | CN1997719B (en) |
| HK (1) | HK1105212A1 (en) |
| WO (1) | WO2006013631A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160105444A (en) * | 2014-01-06 | 2016-09-06 | 크레이튼 폴리머즈 유.에스. 엘엘씨 | Hot melt pressure sensitive adhesive and thermoset comprising styrene-butadiene polymers having high vinyl and high di-block |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010074267A1 (en) * | 2008-12-26 | 2010-07-01 | 日本ゼオン株式会社 | Block copolymer composition and hot-melt adhesive composition |
| CN102264832B (en) | 2008-12-26 | 2014-01-08 | 日本瑞翁株式会社 | Block copolymer composition, film, and process for producing block copolymer composition |
| WO2010098356A1 (en) | 2009-02-27 | 2010-09-02 | 日本ゼオン株式会社 | Block copolymer composition for flexographic printing plates |
| EP2415846B1 (en) * | 2009-03-31 | 2017-11-15 | Zeon Corporation | Adhesive composition for labels |
| JP5533866B2 (en) | 2009-06-30 | 2014-06-25 | 日本ゼオン株式会社 | Elastic film composition |
| US20130245208A1 (en) * | 2012-03-16 | 2013-09-19 | Nitto Denko Corporation | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| TWI504661B (en) * | 2013-11-19 | 2015-10-21 | Chi Mei Corp | Block copolymer composition |
| US10005924B2 (en) * | 2014-02-28 | 2018-06-26 | Zeon Corporation | Transparent adhesive sheet |
Family Cites Families (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4080348A (en) * | 1976-05-18 | 1978-03-21 | Johnson & Johnson | Tacky adhesive |
| US4136071A (en) * | 1976-05-18 | 1979-01-23 | Johnson & Johnson | Mixed block polymer adhesive |
| US4096203A (en) * | 1976-07-30 | 1978-06-20 | Shell Oil Company | Process to control cohesive strength of block copolymer composition |
| JPS60226580A (en) * | 1984-04-25 | 1985-11-11 | Japan Synthetic Rubber Co Ltd | Adhesive composition |
| JPH0689311B2 (en) | 1985-06-05 | 1994-11-09 | 日東電工株式会社 | Pressure sensitive adhesive composition |
| JPH0755999B2 (en) * | 1986-09-05 | 1995-06-14 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Block copolymer composition |
| JPS63248817A (en) | 1987-04-01 | 1988-10-17 | Nippon Zeon Co Ltd | Production of linear block copolymer |
| JPH0798890B2 (en) * | 1989-06-23 | 1995-10-25 | 日本ゼオン株式会社 | Block copolymer composition for pressure-sensitive adhesive and pressure-sensitive adhesive composition |
| US5292819A (en) | 1989-08-11 | 1994-03-08 | The Dow Chemical Company | Radial block copolymers containing butadiene endblock |
| JP2893124B2 (en) | 1990-04-02 | 1999-05-17 | 日本エラストマー株式会社 | Adhesive composition |
| JP3168632B2 (en) * | 1991-10-02 | 2001-05-21 | 旭化成株式会社 | Hot melt type pressure sensitive adhesive composition |
| JP3157256B2 (en) | 1992-03-19 | 2001-04-16 | 旭化成株式会社 | Adhesive resin composition |
| US5342685A (en) * | 1992-05-18 | 1994-08-30 | Minnesota Mining And Manufacturing Company | Hot-melt-coatable adhesives |
| JP3309438B2 (en) * | 1992-09-04 | 2002-07-29 | 日本ゼオン株式会社 | Block copolymer |
| JPH06228522A (en) | 1993-02-03 | 1994-08-16 | Nippon Zeon Co Ltd | Hot-melt pressure-sensitive adhesive composition |
| US5719226A (en) * | 1995-09-15 | 1998-02-17 | Shell Oil Company | Low viscosity hot melt disposables adhesive composition |
| GB2310859A (en) * | 1996-03-08 | 1997-09-10 | Shell Int Research | Adhesive compositions comprising block copolymers |
| US5891957A (en) * | 1996-10-24 | 1999-04-06 | Shell Oil Company | Adhesive composition for skin adhesion and bandage applications |
| US6277488B1 (en) * | 1998-10-28 | 2001-08-21 | 3M Innovative Properties Company | Adhesive composition containing a block copolymer composition and polyphenylene oxide resin and products thereof |
| JP4497579B2 (en) | 1999-04-27 | 2010-07-07 | 日本エラストマー株式会社 | Novel adhesive composition |
| EP1195405A4 (en) * | 1999-06-04 | 2009-07-08 | Kaneka Corp | Curable composition and method of use thereof |
| US6531544B1 (en) * | 2000-02-03 | 2003-03-11 | H.B. Fuller Licensing & Financing, Inc. | Block copolymer based hot melt adhesive for bonding lotion coated substrates |
| JP2001271049A (en) | 2000-03-24 | 2001-10-02 | Nippon Nsc Ltd | Hot-melt tacky agent composition |
| KR100503985B1 (en) * | 2000-05-09 | 2005-07-28 | 아사히 가세이 가부시키가이샤 | Block copolymer composition |
| EP1266935B1 (en) * | 2000-06-30 | 2008-08-13 | Asahi Kasei Kabushiki Kaisha | Styrene copolymer composition |
| WO2002057386A2 (en) * | 2001-01-18 | 2002-07-25 | Kraton Polymers Research B.V. | Adhesive composition |
| US20040077789A1 (en) * | 2002-01-10 | 2004-04-22 | Keiichi Toda | Block copolymer |
| JP4436599B2 (en) * | 2002-10-15 | 2010-03-24 | ヘンケルジャパン株式会社 | Hot melt adhesive and disposable product using the same |
| JP4518742B2 (en) * | 2003-02-07 | 2010-08-04 | 日本エラストマー株式会社 | Novel adhesive composition |
-
2004
- 2004-08-05 US US11/571,909 patent/US8039553B2/en active Active
- 2004-08-05 KR KR1020077001768A patent/KR100874488B1/en active IP Right Grant
- 2004-08-05 EP EP04771282.3A patent/EP1775332B1/en active Active
- 2004-08-05 WO PCT/JP2004/011255 patent/WO2006013631A1/en active Application Filing
- 2004-08-05 CN CN200480043747XA patent/CN1997719B/en active Active
-
2007
- 2007-09-27 HK HK07110489.0A patent/HK1105212A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160105444A (en) * | 2014-01-06 | 2016-09-06 | 크레이튼 폴리머즈 유.에스. 엘엘씨 | Hot melt pressure sensitive adhesive and thermoset comprising styrene-butadiene polymers having high vinyl and high di-block |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1997719A (en) | 2007-07-11 |
| EP1775332B1 (en) | 2019-03-06 |
| EP1775332A1 (en) | 2007-04-18 |
| US20080009587A1 (en) | 2008-01-10 |
| CN1997719B (en) | 2010-05-05 |
| WO2006013631A1 (en) | 2006-02-09 |
| KR100874488B1 (en) | 2008-12-18 |
| EP1775332A4 (en) | 2008-08-20 |
| HK1105212A1 (en) | 2008-02-06 |
| US8039553B2 (en) | 2011-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8563646B2 (en) | Adhesive composition | |
| KR100501986B1 (en) | Block copolymer and composition containing the copolymer | |
| JP3556224B2 (en) | Multi-block hydrogenated polymer for adhesives | |
| JP5942103B2 (en) | Block copolymer composition for adhesive and adhesive composition | |
| JP5572716B2 (en) | Block copolymer for adhesive, method for producing the same, and adhesive composition | |
| KR100830012B1 (en) | Adhesive formulations from radial s-i/bx polymers | |
| US10323164B2 (en) | Hydrogenated block copolymer composition and pressure-sensitive adhesive composition | |
| JP2004520465A (en) | Adhesive composition | |
| JP4518742B2 (en) | Novel adhesive composition | |
| KR20070110432A (en) | Adhesive compositions comprising mixtures of block copolymers | |
| JPH0593176A (en) | Hot-melt self-adhesive composition | |
| JP6704283B2 (en) | Adhesive composition | |
| KR100874488B1 (en) | Pressure sensitive adhesive composition | |
| JP4963796B2 (en) | Block copolymer composition for asphalt adhesive and asphalt adhesive composition | |
| JP2000309767A (en) | Novel hardenable pressure-sensitive adhesive composition | |
| CN1914289A (en) | Low viscosity, hot-melt stable adhesive compositions | |
| JP2008106149A (en) | Block copolymer for asphalt pressure-sensitive adhesive and asphalt pressure-sensitive adhesive composition | |
| JP6147481B2 (en) | Adhesive composition | |
| JPH0598130A (en) | Hydrogenated block copolymer composition and its hot-melt tacky adhesive composition | |
| JP2013082793A (en) | Tacky adhesive composition | |
| JP2009084461A (en) | Adhesive composition for elastic member | |
| JPH0978047A (en) | Hot melt pressure sensitive adhesive composition | |
| JP2019163453A (en) | Block copolymer composition and adhesive composition | |
| JP5063720B2 (en) | Novel adhesive composition | |
| JP2002047469A (en) | Self-adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20121121 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20131118 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20141120 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20151118 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20161123 Year of fee payment: 9 |
|
| FPAY | Annual fee payment |
Payment date: 20171114 Year of fee payment: 10 |
|
| FPAY | Annual fee payment |
Payment date: 20181121 Year of fee payment: 11 |
|
| FPAY | Annual fee payment |
Payment date: 20191120 Year of fee payment: 12 |